Apparatus for halogenation



Aug. 26, 1952 H. J. NOEBELS APPARATUS FOR HALOGENATION Filed June 13, 1950 5 7 23 IIN\.IIENQTOR HemyJafinlVBelfs i I BY ATTORNEY Patented Aug. 26, 1952 UNITED i 1 2,608,66fi

APPARATUS FOR HALOGENATIQN' Help ul: Noebe s, M t mN J' ssignork o ayden ,Qhemi a r atio New York a -i, ah corgorationof Delaware Application June'13; 1950, S eriaLNo. 167,802

inventionirelateslespecially'to an apparatus f or. the shalogenation of alkyl:substitutedcbenzenes. An obj ect of my inventionis toprovide an ap-l-i paratus .for producing.suchaproducts:continuously and whichrmay; be. obtainedzthereby withia higlr uniform yield; t Anothenobject is. to: provideia. column; having a countercurrent .of: liquidand vapor providing ade'quateivapor spaces contain-t ing the gaseous halogen which, accordingly, can be effectively irradiated therein with ultraviolet and visible rays. For instance, this may be accomplished-in an all-glass bubble cap column so modified and* constructed asto provide for conducting the reaction-mainly in the said vapor spaces which are substantiallyunobstructed by light-reflecting and dispersing-fillingmaterials.

I i-accordance with my invention; for example;

I providean apparatusin:which an aromatic .hydrocarbcnis fed intothe upper-"end of an all glass loubble cap plate column having large vapor spaces, effectively irradiatedwith-ultraviolet ra-ys, so as toreact in stoichiometric quantitywith'a halogen admitted in its; vaporform to a, lower portion of the' said column while a mixture of the-products formed-is being withdrawn from the bottom thereof and--hydrocarbon-saturated hy-' drogen chloride is being withdr-awnfromthe top ofithecolumn r With this apparatus it is possible to replace continuously one; twoor-moreof the-- hydrogen atoms in thepalkyl side chainof said hydrocarbon; etc. withhalogen atoms in said vapor spaces, and mainly in the vapor phase, and

t a n m" PPQdiA i ;j ifnnd siredi od..-

cta SF adfi e ant ty u travi le ra s s Well as a unpli di t s oundthat w le; the 'i c st r attl wer emper ures-: 70?" ceeds best and with higher yields at a tempera hove the boiling pointof thejhydro'carbon tu're etc? V -Pre nt a a tus di t nctl d fiie ent.

firem n epistemic Conklin nq gazaesa October 21 19-31 upon-Chlorinationapparatus; in which the reaction is carried out in the liquid phase"" irri 'a cqlhmn packed with glass which with its h rs r Furt er objects of' myi fivention be seen;

fmmg't fe detailed des hereinafter;

lripti'on Of my invention While my inyentio'n lis-Qcapahle of beingcarried I out many'difierent ways an d in; manydifierentg types of apparatuswlhave shown, by way of ill A d5 reflection, refraction and absorption ofj rays is substantially impenetrable to; the'ultraviolet rays-v us'ed "in; cpnducting the reactiqn particularly in lustration, only-one typeof apparatus for use;

which are separated. by iplates 3 oi the same ma terial, having central vapor openings 4. containing largeetubular risers: 5; also of the same. material ana -which extend upwardly into stillzlarger liquid sealed bubble capsifi, made ofthe samematerial and eachl of: which. is: provided with; one: or more" vapor-openingsor slots 1 atathe side thereof away from the upperr end; of: a liquid-conveying downcomer tube; 8; of. large; crossrsection, having a liquid: inlet opening 9; at its. side, located away from the vapor. opening lot the adjacentbubble cap Baas well as-a vertical-guard.Hiwith an um: brella covert ll: attached thereto. situated adjacentttoisaidibubble cap 6; so as topreventthe bubbling and foaming mist; with thelvapor presm surespresent, from disturbing the;.unifor m overflosnaqfathe liquidin-to the downcomei: 8; oflarge. cross=sectional area, which, hasnan. upwardly flared-:1 downwardly, directed: section [2 withinpthe p1ate.x3;leading,to;a: pipe section [3 ofsmaller 'diameter extending through thenext, intervening vaponspace, Whichisvery highI toprovide a large vapor. space.capacity.- for theilarge volume of'nqncondensable gasest. The lower or outlet end .of thetpipei l 3.: isisubmergedin. the liquid present on thesnextplate-i.

Thetcolum'n has: three or moreichlorineinlet.

pipes; 1.6, I11. and: liisprovided with" handvalves I 9 Zlkand: 2 l respectively, and. connected to a 01110,.

rine supply pipe 22, fed with. chlorinetat a con-n stantl pressure andrpreferably preheated, atleast initially, to any desiredtemperatures, f or instance 20to. C., and leading, respectively, to the-first three lower column sections 2- having the said vapor spaces l4 therein, where the reactionprincipally takes place. AlsoLthe sections 2 which, as above stated, are made of Pyrex brandresistant glass No}; 774* or; similar glass'to: withstand heat and yeikbe capable of efiectively; transmittingthe ultraviolet rays, the downcomers 8; the guards no; umbrellas H pipe sections [2.13; bubble caps 6; risers 5* and plates 3; areall made of the ,same; transparentmaterial and are tightly sealed-"and secured to these different parts by gaskets 23 of Teflon, which is polytetrafluoroethylene, the gasketing being the same throughout the entire apparatus, as no other gasketing has been found ,to be, completely effective in withstanding the may be distributed along the entire length of the.

column I, and these are provided with individual control switches. The toluene is constantly fed into the column I through a pip 25, by means of r a constant level supply from a storage tank 26 having an inlet 21, by a pump 28 and a'pipe 29- leading to a constant level feed tank 30, having an overflow pipe 3| leading back to the'supply tank (Apipe' 3-2 having a hand valve .33;,con:.

veys the toluene to a pair of alternative filters 34 and '35 having, respectively, feed pipes Hiand 31 provided with hand valves 38 and39, as JWGH as draw-off pipes 40,and 4|, also provided with hand valves 42 and.43. ,A pip 44 with a hand valve 45'conve'ys the toluene therefrom when de-- sired, through a rotameter 14 of any desired character, having hand valve-controlled inlet .and outlet pipes 46v and 41, to the feed pipe 25, provided 'witha hand valve 48. and a by-pass pipe 49 having. a hand-control valve 50 located between two hand valves and 52. V

The'column I, at the top thereof, has a genchloride produced by the reaction .to-a. Pyrex condenser 54 having a coolingcoil 55 and an .outlet pipe 56 for the eflluent, from which a trapped pipe 51 leads the condensate, comprised almost entirely of toluene, back to the feed pipe 25, whilev a branch pipe 58 leads to any desired hydrogen chloride recovery unit or absorber (not shown) preferably under a vacuum of 1 ofwater to avoid danger from accumulated pressures. Also, a pipe 59, connected to the pipe 58, has hand valve controlled branches 60 and 6| leading, respectively, from. two lead-lined receivers 62 and 6-3hav'ing hand valve controlledair vent pipes.

64 and 65 and hand valve controlled liquid drawofipipestfi and 61, respectively, leading to any desired distillation and/or washing apparatus,

(not shown) for separating the constituentpr'oducts'. The containers 62 and 63 receive the liquid, comprising the halogenation reaction prodnot or products, by:.means. of a trapped pipe 68 connected to'the' bottom of the column Is and having a hygrometer chamber 69 with a handval'ved draw ofi pipe 10, the outlet side of which is connected-Mia pipe H to hand-valved branchpipes" and v'13- leading into. the top of the rex ceivers 62 and 63,'respectively. I

"As particular examples of the procedure in op-.

eeoeeet difierent mercury vapor lamps, is used in an amount of 30.7 watts per part by weight, in pounds for example, of toluene fed, although different proportions can be used, if desired, to illuminate the chlorination area mainly in the lower /3 of the column I'. The temperature of the reaction zone starts at about C. and is maintained approximately between 110-160 C., which temperature should preferably be about 123 C. The hydrogen chloride gas formed during the reaction, after separating the toluene therefrom and returning it to the column I' by the pipe 51, is removed by the pipe 58 to a recovery plate, with the aid of a vacuum of about 1 ",'that is to say preferably from 1 to 3" of water at the top of the column. The control of the column is attained by controlling the feed of the toluene and chlorine, respectively, and the application of the ultraviolet rays to the column.

pipe 53 l forv conveyingithehydrocarbon-saturated hydro,-

eratingthe apparatus made in accordancewith' my invention. I may. for instance and by way 'ofi' illustration, proceed as follows:

5 Ex ample I.--Ohlor inction of toluene parts by weight 'perlhour While chlorine gas, having a temperatureof 2-50 C., is admitted; at

the fourth plate from the bottomlat the-rate or about 50 parts by weight per hour. Ultraviolet radiation, controlled 'by switching ,on or off the When the column has reached equilibrium the product;collected in the receivers G2.and 63 containsuby weight about offlbenzyl chloride; and about-15%. of :benzalf chloride. Consequently, there-is substantially no free toluene or benzotrichloride present. Itis apparent fromtheExample III (a) that, instead, toluene; could be: chlorinated completely as is the p-chlorotoluene, to. the benzotrichlorid-e stage.

Example li -Chlorination of p-xylene v p-Xylene is run by thepipe 25 at the rate ti 51.6 parts by weight per hour into a column I similar to tliat described above but having smaller capacity. .At the same time chlorine is in-' troducedirom the pipe 22- at a lower level in the column at a ratesufiicientto allow for the chlorination of 50% of the xylene to xylylene dichlo-:

The column is illuminated with 3.88 wattsof ultraviolet light per "part by weight o1 'p-fl xylene-fed, by the mercury vapor lamps 24. -During-the-reaction, the reaction zone'of the column ;v

ride.

is maintained at a temperature somewhere between -l70 C., which should preferablybe about C.- The product withdrawn from the bottom of the reactorl contains by weight 12.5 %,.v

of unreacted p-xylene, 60% of p-xylyl chloride, 24.5% of p -xylylene dichloride, and chlorinated materials. I

I llchlo ri'nation of p-chlorotoluene Whenmetal-free p-chlorotoluene is fed"; mto the' top of the-apparatus similar to the one described'above at therate or 238parts b y whileilluminationis provided by sufiicient ultraride.

. Q ELM P lfimB Pw hm e e n ch or ne are fedinto the column I at the rateof 1733 parts, by weight per ;ho ur ;and 330 parts by weight per, hql11j,; 1@espectively. The temperature of-the re: action zone is maintained at from,lf1 0. tol70f C., and which should preferably be at about 1 60 c1, whil e illuminatiorr is: provided y ultraviolet radiation. The product withdrawn from the bot m of t e o iwnta eby e h or hle .cla m ch ori (5% a p-ch ombee al l fifi n %1 -tlil rqw e; I 2 .1 ;.'I

3% of higher cgeoacco Example I VQ- Chlorination of Q- QZLZOTOtOZUG'ILC 1950 parts by weight pei hour while 370 par ts by'weight of chlorine-pen hour is admitted to the fifth p a f om i i bq wmr Elb -t in the reaction zone is maintained at from 120 to lfI?"Ci,"and which should preferably be at about 160 C. The product obtained when the'columns have reached equilibrium is distilled, and the cut boiling attic- 56 C. at2 mm. pressure when. degassed and 'redistilled, is found toljcontain by weight 94% of o-chlorobenz'yl chloride and" 6% of o-chlorobemal chloride. No o-chlorobenzotrichloride or o-chlorotoluene is found in the product.

In the applicants apparatus, in view of the fact that the reaction of halogenation takes place mainly in the vapor phase, that is to say in the large capacity vapor spaces I4, where the vapors present contain a larger percentage of the hydrocarbon or other compounds to be chlorinated than the liquid on the plates 3, respectively, a more effective and complete halogenation is accomplished, inasmuch as the droplets of the halogenation product formed therein coalesce and are being continually removed from the vapor spaces to be added to the body of liquid beneath the same on each plate, while these droplets are being replaced by the hydrocarbon vapors, which are at a temperature above the boiling point of drocarbon being fedshould bemaintained, as far; "as possiblefor thebestresults; #Furthermore, the purity of-irthexrawimaterials usedis of great importance.in ordento obtain the desired strength of the products 'and even 'in starting-the reaction; -=Chlori1ierhade by thelect'rolytic process and "freed of inorganicl con taminantsis found to be-ve'ry suitablez A good grade of'c'oal' tar toluene with a -fairly narrow boiling range ver y suitable 'e'special'ly if "fre'ed of-= Water and impurities such as iron er other metal ions,- which may undesirablyicatalyze the chlorinatiomq Lei"... i: l While I have described my invention abs-vars detail I *wish'it to be understood that many changes may be made therein withoutdepartlng fromthe spirit ofthesama L '1 1 An apparatus for producing a li alo-alkyl substituted benzenawhich comprises an all-glass bubble cap column accessible to actinic rays having successive plates with interconnecting liquidconveying downcomers, the lower portion of said downcomers being located below the liquid surface of the lower plate, the vapor space between said plates predominating over the liquid capacity, and in which the bubble caps are free from vapor openings near said downcomers.

2. An apparatus for producing a halo-alkyl substituted benzene, which comprises an allglass bubble cap column accessible to actinic rays having successive plates with interconnecting liquid-conveying downcomers, the lower portion the latter. I have found that the compound 7 which exists in the greatest concentration in the vapor phase will be chlorinated to the greatest extent, and as toluene has a higher vapor pressure than benzyl chloride, this avoids as far as possible introducing more than the desired number of halogen atoms intothe compound to be chlorinated. For instance, the condensation is such as to remove continually benzyl chloride from the vapors before benzal chloride is formed therefrom. Also, the high yield obtained is aided, for instance, by controlling, in the vapor phase to between 110 and 160 C. in toluene chlorination, the temperature of the reaction, which, however, takes place from 10 C. up to the reflux temperature of the final product, although the minimum starting temperature is preferably not below to C. However, the lower the temperature the less will be the rate of chlorination. Also, the intensity and position of the ultraviolet lamps used is important in contributing to the best results as to yields and in eifectively penetrating the vapor spaces, which are substantially unobstructed by liquid and solid materials that would tend to divert or disperse disadvantageously the ultraviolet rays by reflection, refraction, absorption, etc. Under these circumstances, I do not find it necessary to illuminate the column uniformly as it is found satisfactory to illuminate principally'thelower third part of the column startingat the lowermost chlorine feed plate and extending upwardly therefrom. Furthermore, too much of the ultraviolet light causes the column torun unsteadily and with a lack of uniformity, whereas too little light, or in the wrong location, will tend to delay or prevent the reaction from starting or will not allow stable equilibrium conditions to be attained therein. Furthermore, conditions approaching the stoichiometric ratio of the halogen and hyof said downcomers being located below the liquid surface of the lower plate, the vapor space between said plates predominating over the liquid capacity, and in which the bubble caps are free from vapor openings near said downcomers, the bubble caps being provided with slots for this purpose located on their sides opposite to the location of said downcomers.

3. An apparatus for producing a halo-alkyl substituted benzene, which comprises an all-glass bubble cap column accessible to actinic rays, the vapor space between the plates predominating over the liquid capacity and in which the successive plates are interconnected by liquid conveying downcomers, the lower portion of said downcomers being located below the liquid surface of the lower plate, said downcomers having flared upper ends provided with umbrella like covers supported from said upper ends by shields at their sides located near said bubble caps.

4. An apparatus for producing a halo-alkyl substituted benzene, which comprises an all-glass bubble cap column accessible to actinic rays having successive plates with interconnecting liquidconveying downcomers, the lower portion of said downcomers being located below the liquid surface of the lower plate, the vapor space between said plates predominating overthe liquid capacity, and in which the bubble caps are free from vapor openings near said downcomers, selective ultra-violet ray lamps beinglocated externally to the lower end of said column.

5. An apparatus for producing a halo-alkyl substituted benzene, which comprises an all-glass bubble cap column accessible to actinic rays having successive plates with interconnecting liquidconveying downcomers, the lower portion of said downcomers being located below the liquid surface of the lower plate, the vapor space between said plates predominating over the liquid capacity, and in which the bubble caps are free from vapor openings near said downcomers, said bubi 8. ble caps being -.prov1ded:.wlth slotstfor-thispur- I I 7 H pose located on thelrisldes opposite to the loca- :REFER'ENCES CITED- fioh Said downwmelis'and Selective ultm'fviolet The following references are of record in the gyililnpslare10cated;,externally;to the lower end m f g ag gf 1. v U .o sa qcocumn-q-4.2-1;-

1 .c 5 a apparatus or producing a halo-alkyl .1 .7. a substitutedbenzene, which comprises an all-glass Number r Name Dat bubble capcolumn accessible to actinlc rays, the 1,432,761 Koch Oct. 24, 1922 yapor;; spac1ez between the plates predominating 2,396,900 Taggart, Jr. ,Marl 19, 1946 overt e liquid. c pacity a d i which he cces- 1o r Y siver t e interconnec by liquid conveying V 1 FOREIGN PATENTS downcomers, the 'lowerportion of saiddownum e U FIYV a V p comers being located below the liquidsurface of 435,656 ce Mel'- L 191? the lower plate, said downcomersjhaving flared V fj REFEWREN'CEMSNIQ7L upper ends provided with umbrella like covers 15 supported ;from said upper ends by shields at their sides located near said bubble caps andselective ultra-violet ray lamps are located externally to the'lower end of saidcplumn. r v

w a HENRY .LNOEBELS. 20

Glass Works. Corning, N. Y., June 1934.

Glass Color Filters, Catalog G ll 2, Coriilhg 

1. AN APPARATUS FOR PRODUCTING A HALO-ALKYL SUBSTITUTED BENZENE, WHICH COMPRISES AN ALL-GLASS BUBBLE CAP COLUMN ACCESSIBLE TO ACTINIC RAYS HAVING SUCCESSIVE PLATES WITH INTERCONNECTING LIQUIDCONVEYING DOWNCOMERS, THE LOWER PORTION OF SAID DOWNCOMERS BEING LOCATED BELOW THE LIQUID SURFACE OF THE LOWER PLATE, THE VAPOR SPACE BETWEEN SAID PLATES PREDOMINATING OVER THE LIQUID CAPACITY, AND IN WHICH THE BUBBLE CAPS ARE FREE FROM VAPOR OPENINGS NEAR SAID DOWNCOMERS. 